Trinuclear dyes for photographic elements



- 3,335,010 United States Patent 0 ice Patented Another object is to provide improved photographic 3,335,010 silver halide emulsions that are sensitized by our valuable TRINUCLEAR DYES FOR PHOTOGRAPHIC trinuclear dyes which are distinguished from other dyes ELEMENTS by having at least one secondary amino substituted alkyl Robert C. Taben and Leslie G. S. Brooker, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey 5 group attached to at least one acidic nucleus in the dye.

Still other objects will become apparent from the follow- No Drawing. Filed May 4, 1964, Ser. No. 364,780 ing Specification and q (31 m (C1, 96 .84) These and other 0b]BCtS are accomplished according to our invention by the synthesis and use in photographic This application relates to photographic sensitizing dyes 10 elements of our trinuclear dyes which include those and more particularly to trinuclear sensitizing dyes havrepresented by the formulas:

I E I R1\'i (-CH=O H 1-14: =0 H-CR )n-1=1\ o=oH (=CHGH) =1; I-R;

I --z i%-NY (|J-NY RI\ T(CH=CH)i-1-b(=CHCR1)n-1=C\ d= /o=n and III --Z "z.

ing at least one acid nucleus substituted with at least wherein R and R each represent an alkyl group having one secondary amino substituted alkyl group, to photofrom 1 to 8 carbon atoms, e.g., methyl, sulfoethyl, cargraphic silver halide emulsions sensitized with said dyes, boxyethyl, hydroxypropyl, sulfobutyl, carboxybutyl, hexyl, and to photographic elements containing said dyes. octyl, etc.; Z and Z each represent the nonmetallic atoms It is known to use trinuclear dyes, such as complex required to complete a 5 to 6 membered heterocyclic cyanine dyes, complex merocyanine and holopolar dyes nucleus such as those selected from the nuclei consistas optical sensitizers in photographic silver halide emuling of those of the thiazole series (e.g. thiazole, 4-methylsion layers. Spectral sensitizing dyes are needed for 40 thiazole, 4-phenylthiazo1e, S-methylthiazole, S-phenylextending (to longer wave length) the sensitivity of thiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2- silver halide emulsions in various photographic materials thienyl)thiazole, etc.), those of the benzothiazole series, including multicolor elements used for color photography. (e.g. benzothiazole, 4-chlorobenzothiazole, S-chlorobenzo- Sensitizing dyes must not only produce the desired sensithiazole, 6 chlorobenzothiazole, 'I-chlorobenzothiazole, tizing characteristics, but must be readily soluble, prefi4-methylbenzothiazole, S-methylbenzothiazole, 6-methylerably in aqueous media for'ease in sensitizing a photobenzothiazole, S-bromobenzothiazole, fi-bromobenzothiagraphic emulsion and also for ease in removal from the zole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4- emulsion layers during the photographic processing so methoxybenzothiazole, S-methoxybenzothiazole, 6-meththat a minimum of stain is produced in the resulting oxybenzothiazole, S-iodobenzothiazole, 6-iodobenzothiaphotograph. The requirement for minimum stain is parzole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetraticularly important in color photographic prints, hydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-di- It is also known to use certain bleachable dyes in lightoxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-

filtering hydrophilic colloid layers in light-sensitive photohydroxybenzothiazole, etc.), those of the naphthothiazole graphic elements. Such light-filtering layers may be series, (e.g. a-naphthothiazole, 3-naphthothiazole, S-methcoated over the light-sensitive layer, between two differoxyfi-naphthothiazole, S-ethoxy fi-naphthothiazole, 8- ently sensitized light-sensitive layers, between a lightmethoxy-a-naphthothiazole, 7-methoxy-u-naphthothiazole, sensitive layer and the support on the side of the support etc.), those of the thionaphtheno-7,6,4,5-thiazole series opposite to the side bearing a light-sensitive layer. Dyes (e.g. 4'-methoxythianaphtheno-7,6',4,S-thiazole, etc.), useful for filter layers must not only absorb light of the those of the oxazole series (e.g. 4-methyloxazole, S-methyldesired wavelengths but must be readily bleachable and/ or Xa O e, 4-phenyl0Xaz0le, 4,5-diphenyloxazole, 4-ethyloxaremovable during the normal photographic processing zole, 4,5-dimethyloxazole, 5-phenyloxazole, etc.), those operations. of the benzoxazole series (e.g.) benzoxazole, 5-chloro- Trinuclear dyes having desirable spectral sensitizing benzoxazole, S-methylbenzoxazole, S-phenylbenzoxazole, characteristics and good solubility in aqueous media are 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-didesired. methylbenzoxazole, 5 methoxybenzoxazole, S-ethoxy- It is therefore an object of our invention to provide benzoXazole, 5-chlor0benzoXazole, 6-methoxybenz0xazole, a new class of valuable trinuclear dyes including complex S-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.) those cyanine dyes, complex merocyanine dyes and holopolar of the naphthoxazole series (e.g. u-naphthoxazole, B- dyes that are good spectral sensitizers and which because naphthoxazole, etc.), those of the selenazole series, (e.g. of their high solubility in aqueous media leave less strain 4-methylselenazole, 4-phenylselenazole, etc.), those of the in photographic elements containing them than dyes benzoselenazole series (e.g. benzoselenazole, S-chloroknown previously. benzoselenazole, S-methoxybenzoselenazole, S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), those of the naphthoselenazole series (e.g. a-naphthoselenazole, fl-naphthoselenazole, etc.) those of the thiazoline series (e.g. thiazoline, 4-methylthiazoline, etc.), those of the 2- pyridine series (e.g., 2-pyridine, S-methyl-Z-pyridine, etc.), those of the 4-pyridine series (e.g., 4-pyridine, 3-methyl- 4-pyridine, etc.), those of the 2-quinoline series (e.g., 2- quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6- chloro-Z-quinoline, 8-chloro-2-quinoline, 6-methoxy-2- quinoline, 8-ethoxy-2-quinoline, '8-hydroXy-2-quinoliue, etc.), those of the 4-quinoline series (e.g., 4-quinoline, 6- methoXy-4-quinoline, 7-methyl-4-quinoline, 8-chlor0-4- quinoline, etc.), those of the l-isoquinoline series (e.g., l-isoquinoline, 3,4-dihydro-l-isoquinoline, etc.), those of the 3-isoquinoline series (e.g., 3-isoquinoline, etc.), those of the 3,3-dialkylindolenine series (e.g., 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindlenine, etc.), those of the imidazole series (e.g., imidazole, l-alkyl imidazole, 1-alkyl-4-phenylimidazole, 1-alkyl-4,5- dimethylimidazole, etc.), those of the benzimidazole series (e.g., benzimidazole, l-alkyl-benzimidazole, 1-alkyl-5,6- dichlorobenzimidazole, etc., those of the naphthimidazole series (e.g., 1-alkyl-a-naphthimidazole, l-alkyl-fi-naphthimidazole, 1-alkyl-5-methoXy-fl-naphthimidazole, etc.), etc.; j represents an integer of from 1 to 2; R represents the hydrogen atom, an alkyl group (e.g. methyl, ethyl, butyl, etc.) or an aryl group (e.g., phenyl, tolyl, etc.); n represents an integer of from 1 to 4; Y and Y each represent a group such as, the hydrogen atom, an alkyl group (e.g., methyl, methoxyethyl, butyl, etc.), an aryl group (e.g., phenyl, tolyl, etc.), a

group, such that at least one of the groups Y and Y contains a group with a tertiary nitrogen atom; q represents an integer of from 2 to 4; R R and R each represents an alkyl group (e.g., methyl, propyl, butyl, hexyl, etc.); W and W each represent a group selected from the oxygen atom, the sulfur atom, the selenium atom and a NR group wherein R represents an alkyl group (e.g., methyl, ethyl, butyl, etc.), an aryl group (e.g., phenyl, tolyl, etc.), etc.; p represents an integer of from 1 to 2; x represents an acid group (e.g., chloride, bromide, iodide, perchlorate, sulfamate, thiocyanate, p-toluenesulfonate, benzenesulfonate, methylsulfate, etc.); D and D each represent a group such as the sulfur atom the selenium atom, or the oxygen atom; m represents an integer of from 1 to 2; Q represents a group,

group, a

N .C t3

group and a CNC- 3 l 3,

group; and R represents a group, such as, any of the groups used on the 3-position of 2-pyrazoline-5-ones, e.g., hydrogen, alkyl (e.g., methyl, isopropyl, tetiary butyl, heXyl, etc.), aryl (e.g., phenyl, tolyl, halophenyl, etc.), amino (e.g. methylamino, diethylamino, phenylamino, etc.), carbonamido (e.g., ethylcarbonamido, phenylcarbonamido, etc.), sulfonamido (e.g., butylsulfonamido, phenylsulfonamido, etc.), sulfamoyl (e.g., propylsulfamoyl, etc.), carbamoyl (e.g., ethylcarbamoyl, phenylcarbamoyl, etc.).

Our dyes are readily soluble in aqueous media, especially in the presence of one equivalent of acid, and are used to advantage to spectrally sensitize photographic hydrophilic silver halide emulsions. The dyes are valuable because of their sensitizing characteristics and their solubility which makes them easy to incorporate in photographic emulsions and also makes it easier to more completely remove the dyes during the processing operations.

The dyes of Formula I are prepared to advantage by reacting a merocyanine dye having the formula:

wherein R, Z, i, R n and W are as defined previously and L represents a Y or a Y group and when this group represents a substituted amino alkyl group, said group is advantgageously a hydro salt of the amine, with dimethylsulfate and dimethylformamide and then reacting the quarternary salt product with a compound having the formula:

wherein Z p, R and x are as defined previously, preferably by heating in a suitable solvent in the presence of a basic condensing agent, e.g., the trialkylamines (e.g., tn'ethylamine, tributylamine, etc.), the dialkylanilines (e.g., N,N-dimethylaniline, N,N-diethylaniline, etc.), heter'ocyclic tertiary amines (e.g., pyridine, quinoline, N-alkylpiperidines, etc.), alkali metal alcoholates (e.g., sodium ethylate, etc.).

The dyes of Formula II are prepared to advantage by reacting a compound of Formula IV with dimethyl sulfate and dimethylformamide, then condensing the quarternary salt product with a compound having the formula:

wherein W, W and L are as described previously. The condensation is carried out to advantage in an inert solvent in the presence of a basic condensing agent (described previously herein). Heating the reaction mixture to the reflux temperature is advantageous.

The dyes of Formula III are prepared to advantage by condensing a dye of formula:

wherein R, Z, 1', Y and Q are as defined previously, with a cyclammonium quaternary salt having the formula:

vrn

wherein R x, Z and p are as described previously and R represents an alkly group (e.g., methyl, ethyl, benzyl, etc.) or an aryl group (e.g., phenyl, tolyl, etc.). The reaction is conducted advantageously in an inert solvent in presence of a basic condensing agent (described previously) and is aided by heating up to the reflex temperature of the reaction mixture.

The dyes of Formula IV where n is 1 are prepared by condensing a cyclammonium quaternary salt having the formula:

IX --Z wherein R, x, Z, i and R are as defined previously with an intermediate having the formula:

wherein W and Y are as defined previously, in an inert solvent, preferably in the presence of a basic condensing agent and preferably by heating.

The dyes of Formula IV in which n is from 2 to 4 are prepared to advantage by condensing a cyclammonium quaternary salt having the formula:

XI --Z wherein R, x, Z, 1', R and n are as defined previously, I represents a group, a SR group or a halogen atom (e.g., chlorine, bromine, etc.); R represents'the hydrogen atom, an alkyl group, or the acyl group of'a carboxylic acid, and R represents an aryl group or R and R together represent the nonmetallic atoms necessary to complete a heterocyclic nucleus (e.g., a piperidine, a morpholino group, etc.) and R represents a lower alkyl group, with a compound of formula X. I

The dyes of Formula VII are prepared to advantage by condensing a compound of Formula XI in which R is a methyl group and n=2, with a compound having the formula:

wherein Q and Y are as defined previously.

Including among the dyes of Formula I are the following typical examples:

DYEI

2 [(2-benzothiazolylethoperchlorate)methylene]-3-(3-dimethylam inopropyl) [(1 methylnaphth0[1,2 d]

thiazolin 2 ylidene) 1 phenylethylidene] 4 thiazolidinone 2)aN( Hs)2 S 2.1 g. (1 mol.) of 3-(3-dimethylaminopropyl)-5-[(1- methylnaphtho[1,2 d] thiazolin-Z-ylidene) -l-phenylethylidene]rhodanine hydroperchlorate was added to 10 ml. of dimethylsulfate and 10 ml. of dirnethylformamide, the mixture heated gently until solution was complete and allowed to stand at room temperature for 1 hour. The product was precipitated with ether and washed with ether.

7 The oily residue was dissolved in 30 ml. of pyridine and I decomposition.

DYE 2 2 [(5 chloro-Z-benzothiazoylyethoperchlorate)methylene] 3- (S-dimethylaminopropyl) -5- (1 -methylnaphtho [1,2-d]thiaz0lin 2 ylia'ene) 1 phenylethylidene1- 4-thiazolidin0ne 2.1 g. (mol.) of 3-(3-dimethylaminopropyl)-5 [(1- methylnaphtho[1,2 dJthiazolin 2-ylidene)-1-phenylethylideneJrhodanine hydroperchlorate was added to 6 ml. of dimethylsulfate and 4 ml. of dimethylformamide and the solution heated gently over an open flame until a faint odod of methyl mercaptan was detected. The reaction mixture was cooled and 10 ml. of pyridine was added. After the exothermic reaction had subsided the solution was treated with 2.6 g. (1 mol.+%) of 5-chloro-3-ethyl-2- methylbenzothiazolium p-toluenesulfonate, 2 ml. of triethylamine and the solution warmed gently for 2 minutes. The mixture was poured into 40 ml. of methanol, made basic with piperidine and chilled. The dye was twice recrystallized by dissolving in dimethylformamide and precipitating with methanol containing dissolved sodium perchlorate. The dye was obtained (yield 36%) as green crystals of MP. 2'6-2264 with decomposition.

DYE3

2 ['(2 benzoxazoylymethoperchlorate)methylene] 3- (3 dim'ethylam'inopropyl) 5 [(1 methylnaphtho [1,2-d1thiazolin 2 ylidene) 1 phenylethylidene1-4- thiazolidinone (CH2)3N(CH3): O C-N /O\ C=CHC=C/ \C=OHC C10 9 d H s \\ea/ 4 Ilq ll 5 N l CH3 HB This dye was prepared by the method used to make dye 2 but by substituting an equivalent amount of 3-ethyl- Z-methylbenzoxazolium iodide for the 5-chloro-3-ethy1-2- methylbenzothizolium p-toluenesulfonate. The twice recrystallized dye was obtained (yield 36%) as green crystals of M.P. 262-264 C. with decomposition.

Included among the dyes of Formula II are the following typical examples:

DYE 4 3 (3 dimethylaminopropyl) 2 [3 (3 dimethylaminopropyl) 4 x0 2 thioxo thiazolidinylidene] 5 [(1 methylnaphth0[1,2 d] thiazolin 2- ylidene) -1-phenylethylidene] -4-thiazolidinone 2)a a)2 2)3 a)2 1.03 g. (1 mol.) of 3-(3-dimethylaminopropyl)-5-[(1- methylnaphtho[l,2 d]thiazolin 2 ylidene) 1 phenylethylidene]rhodanine hydroperchlorate was added to 5 ml. of dimethylsulfate and 2 ml. of dimethylformamide and the solution heated gently over a flame until a slight odor of methyl mercaptan was detected. The reaction mixture was then cooled and treated with 5 ml. of pyridine. After the exothermic reaction had subsided the mixture was treated with 1.0 g. (1 mol.|-100%) of 3-(3- dimethyla-minopropyl)rhodanine hydroperchlorate and 2 ml. of triethylamine and warmed gently for approximately 2 minutes. The reaction mixture was poured into a solution containing 40 ml. of methanol and 5 ml. of piperidine and the solution chilled. The dye was collected on a filter and dried. The dye was twice recrystallized by dissolving in dimethylformamide and precipitating by the addition of methanol. The dye was obtained (yield 12%) as green crystals with gold reflex of M.P. 265267 with decomposition.

DYE 5 2 [3 (2 dimethylaminoethyl) 4 0x0 2 thioxo- 5 thiazolidinylidene] 3 (3 dimethylamin0pr0pyl)- 5 [(1 methylnaphth0[1,2 d]thiazo lin 2 ylidene)- I-phenylethylidene]-4-thiaz0lidin0ne s 2)aN( a)2 (CHM 3):

This dye was prepared by the method used for dye 4 but substituting an equivalent of 3-(2-dimethylaminoethyl)rhodanine hydroperchlorate for the rhodanine used to make dye 4. The recrystallized dye was obtained (yield 22%) as green crystals of coppery reflex of M.P. 273- 275 C. with decomposition.

DYE 6 3 (3 diethylam'inopropyl) 2 [3 (3 dimethylaminopropyl) 4 0x0 2 thz'oxo 5 thiazolidinylidene} 5 [(1 ethylnaphtho[1,2 d]thiqz0lin 2 ylidene)- -ph enylethylidene] -4-thiazolidinone 2)aN(Cz s)2 2)a Ha)z 2.46 g. (1 mol.) of 3-(2-m-orpholinoethyl)rhodanine, 5.82 g. (1 mol.) of 5-[(3-ethyl-2-benzothiazolinylidene) ethylidene] 2 methylmercapto 4 oxo 3 phenyl- 2-thiazolinium p-toluenesulfonate and 3.08 ml. (2.2 mol.) of triethylamine were added to 25 ml. of acetic anhydride and heated under reflux with stirring for 5 minutes. The

' reaction mixture was cooled and poured with stirring into 300 ml. of ether. The dark green tar which separated was washed with ether and Was then stirred with hot acetone. The acetone suspension of the dye was chilled, diluted with ether and filtered. The dye was recrystallized by dissolving in dimethylformamide and diluting with methanol. The dye was twice more recrystallized by dissolving in pyridine and diluting with methanol. The dye was obtained (4%) as dark green crystals of M.P. 3l0 C.

DYE 8 5 [(1 ethylnaphtho[1,2 d] thz'azolin 2 ylidene) 1- phenylethylene] 3 (2 morpholinoethyl) 2 [3- (2 morpholino'ethyl) 4 0x0 2 thioxo 5 thiazolidinylidene]-4-thiaz0lidin0ne This dye was prepared as dye 7 but from a molar equivalent of quaternized 5-[(1-ethylnapht-ho[1,2-d]thiazolin- 2 ylidene) 1 phenylethylidene] 3 (2 morpholinoethyl)rhodanine. The solid dye product was washed with boiling benzene and with boiling toluene then recrystallized twice by dissolving in pyridine and diluting with benzene. The dye was obtained (13% yield) a purple crystals with a gold reflex of M.P. 245247 C. with decomposition.

DYE 9 1 (2 diethylaminoethyl) 5 [(1 ethylnaphtho[1,2- d]thiazolin 2 ylidene) (1 methylnaphth0[1,2 d] thiazolin 2 ylidene)is0propylidene] 3 phenyl 2- thiobarbituric acid A mixture of 1.0 g. (1 mol.) of 1-(2-diethylaminoethyl) 5 1 ethylnaphtho[1,2 d]thiazolin 2 ylidene)isopropy1idene] 3 phenyl 2 thiobarbituric acid, 1.3 g. (1 mol.+% excess) of 1-methyl-2-methylthionaphtho[l,2-d]thiazolium p-toluenesulfonate and .4 g. (1 mol.+100% excess) of triethylamine was heated at the refluxing temperature in 25 ml. of pyridine for ten minutes. The resulting solution was cooled and poured into ether and the precipitate was collected on a filter and the solid was washed with ether. The crude dye was dissolved in 600 ml. of hot pyridine, the solution was filtered hot, methanol was added and after chilling the dye was collected on a filter. The yield of dye after another like treatment was 14%. The shiny green crystals had a M.P. 300 C.

DYE 10 I (2 diethylaminoethyl 5 [di(1 ethylnaphtho[1,2- d]thiazolin 2 ylidene)ispr0pylidene] 3 phenyl- Z-thiobarbituric acid This dye was prepared as dye 9 but by substituting a molar equivalent of 1-ethyl2-ethylthionaphtho[1,2-d]' thiazolium ethylsulfate for the intermediate used for dye 9. The twice recrystallized dye was obtained (8% yield) as shiny green crystals of M.P. 291-292 C. with decomposition.

DYE ll 1 (2 diethylaminoethyl) [(1 ethylnaphtho[1,2- d]thiazolin 2 ylidene) (1 methylnaphth0[1,2-d] thiazolin 2 ylidene)is0pr0pylidene] 3 phenylbarbituric acid This dye was prepared like dye 9 but using as the parent dye 1- (Z-diethylaminoethyl) -5-[ l-ethylnaphtho [1,2 d]thiazolin 2 ylidene)isopropylidene] 3- phenylbarbituric acid in place of the corresponding thiobarbituric acid containing dye. The recrystallized dye was obtained yield) as green crystals of M.P. 300- 302 C. with decomposition.

DYE 12 1 2 diethylaminoethyl) 5 [di(1 ethyln aphtho [1,2 d]thiazolin 2 ylidene)is0pr0pylidene] 3- phenylbarbituric acid This dye was prepared like dye 11 but by substituting 1 ethyl 2 ethylthionaphtho[1,2 d]thiazolium ethyl sulfate for the cyclammonium quaternary salt used to make dye 11. The recrystallized dye was obtained 21% yield) as green crystals of M.P. 298-299 C. with decomposition.

The intermediates having Formulas V, VIII, IX and XI are well known in the art. The syntheisis of intermediates having formulas IV, VI, X and XII are illustrated with descriptions of representative intermediates used in preparing our dyes.

3 (3 dimethylaminopropyl) 5 [(1 methylnaphtho [1,2 d]thiazolin 2 ylidene) 1 phenylethylidene1- rhodanine hydroperchlorate 14.8 g. (1 mol.) of 2-(l-chlorostyryl)-1-methyliiaphtho [1,2-d]thiazolium chloride and 2.8 g. (1 mol.) of 3-(3- dimethylaminopropyl)rhodanine hydroperchlorate were dissolved in 80 ml. of dimethylformamide and the solution treated with 16.8 ml. of triethylamine and the solution heated at reflux for 5 minutes. The hot reaction mixture was filtered and the filtrate treated with a solution of 5.0 g. of sodium perchlorate in 100 ml. of ethanol, made acid with acetic acid and chilled. The dye was collected on a filter and recrystallized by dissolving in dimethylformamide and precipitating with ethanol containing dissolved sodium perchlorate. The dye was obtained (yield 59%) as green crystals of M.P. 236-238 with decomposition.

3- (3-diethylamin'opropyl) rhodamne hydroperchlorate 22.6 g. (1 mol.) of bis(carboxymethyl)trithiocarbonate chloric acid and concentrated to a viscous oil on the rotary evaporator. The oil was dissolved in 70 ml. of water and treated with a solution of 18.3 g. of sodium perchlorate in 50 ml. of water and chilled. The product separated as a heavy oil which was washed once with a small portion of water containing dissolved sodium perchlorate and three times with isopropyl alcohol. After washing, the last traces of isopropyl alcohol were removed under vacuum. The product was then made crystalline by stirring with a small amount of methanol and obtained (yield 35%) as pinkish crystals of M.P. 102-104" with decomposition.

3-(2-dimethylamin0ethyl)rhodanine hydroperchlorate This was prepared by the same reaction used to prepare the preceding intermediate but by using N,N-dimethylethylenediamine.

3 (3 diethylaminopropyl)-5-[1 ethylnaphth0[1,2 d]- thiazolin 2 ylidene) 1 phenylethylidenelrhodanine hydroperch'lorate 15.0 g. (1 mol.) of 1-ethyl-2-(2-ethylthiostyryl)naphtho [1,2-d]thiazolium ethylsulfate and 10.2 g. (1 mol.) of 3 (3 diethylaminopropyl)rhodanine hydroperchlorate were dissolved in 50 ml. of dimethylformamide and 9 ml. of triethylamine and the solution heated on the steam bath for 1 hour. The reaction mixture was poured into a solution containing 100 ml. of methanol and 10 ml. of piperidine and chilled. The dye was collected on a filter and dried. The dye was recrystallized by dissolving in dimethylformamide and precipitating with methanol. The dye was obtained .(yield 56%) as green crystals of M.P. 196-197 with decomposition.

1 (2 diethylaminoethyl) 5 [(1 ethylnaphtho [1,2 d]thiazolin 2 ylidene)isopropylidene] 3- phenyl-Z-thiobarbituric acid A mixture of 8.4 g. (1 mol.) of I-(Z-diethylaminoethyl) 3 phenyl 2 thiobarbituric acid hydroperchlorate, 8.0 g. (1 mol.) of 1-ethyl-2-methylnaphtho- [1,2-d]thiazolium p-toluenesulfonate and 3.6 g. (1 mol.+ 100% excess) of ethyl orthoacetate was heated at the refluxing temperature in 50 ml. of pyridine for three minutes. The reaction mixture was poured into water, the resulting precipitate was collected on a filter, washed with water and dried. The solid was dissolved in 300 ml. of hot pyridine, and 2.8 ml. of triethylamine and 300 ml. of methanol were, added. After chilling, the dye was collected on a filter. After another such purification the yield of dye was 11%. The orange crystals had a M.P. of 260- 261 C. with decomposition.

1- (2-diethylaminoethyl) -3-p'henyl-2-thio barbituric acid hydroperchlorate A solution of 67.5 g. (1 mol.) of phenylisothiocyanate in 100 ml. of benzene was added dropwise with stir-ring to a solution of 58.5 g. (1 mol.) of N,N-diethylethylenediamine. The reaction was exothermic. The whole was allowed to stir at room temperature for 2 hours and then 200 ml. of ethanolic HCl g./l.) was added. The resulting solution was concentrated using a rotary evaporator. The residue was recrystallized from 600 ml. of ethanol. The yield of I-(Z-diethylaminoethyl)-3-phenyl- 2-thiourea hydrochloride was 90%.

A solution of 28.2 g. (1 mol.) of malonyl dichloride in ml. of chloroform was added dropwise with stirring to 57.4 g. (1 mol.) of 1-(2-diethylaminoethyl-3-phenyl- 2-thiourea hydrochloride in 200 m1. of chloroform. After the addition had been completed the whole was heated on a steam bath for one hour. The resulting mixture was concentrated using a rotary evaporator. To the residue dissolved in, water, a water solution of 49' g. (1 mol.+100% excess) of sodium perchlorate was added. The solid that precipitates was collected on a filter, washed with water and dried. The yield after one rel 1 crystallization from dimethyl-formamide-ethanol mixture was 64% and the colorless crystals had a M.P. of 224- 225 C. with decomposition.

(Z-diethylaminoethyl) -5-[ (Z-ethylnaph tho [1,2-d] thiazlin-2-ylidene) isopropylidene] -3-phenylbarbituric acid 1-(Z-diethylaminoethyl)-3-phenylbarbituric acid hydroperchlorale This was prepared like the corresponding thiobarbituric acid salt by using phenyl isocyanate in place of phenylisothiocyanate. The recrystallized intermediate was obtained (56% yield) as colorless crystals of M.P. 223- 224 C. with decomposition.

Our dyes are used to advantage to optically sensitize silver halides, e.g., silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc. dispersed in any of the hydrophilic colloids known to be satisfactory for making lightsensitive photographic emulsions. Useful hydrophilic colloids include natural materials, e.g., gelatin, albumin, agar-agar, gum arabic, alginic acid, etc., and synthetic materials, e.g., polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, etc.

The concentration of our dyes in the emulsions can vary widely, i.e., from about 5 to about 100 mg. per liter of flowable emulsion. The specific concentration will depend upon the dye, the type of light-sensitive material in the emulsion and the particular efi'ects desired. The most advantageous dye concentration for any given emulsion can be readily determined by making the concentration series and observations customarily used in the art of emulsion making.

As mentioned previously our dyes are readily soluble in water especially in the presence of one equivalent of acid. The hydrophilic colloid-silver halide emulsion is sensitized to advantage by adding the appropriate amount of dye in aqueous solution to the emulsion with intimate mixing to insure uniform distribution. Any of the other methods customarily used in the art can be used for incorporating our dyes. For example, the dyes can be incorporated by bathing a photographic element coated with the emulsion, in a solution of the dye. Photographic elements that have a silver halide film coating (deposited from the vapor state under vacuum) are also sensitized to advantage by bathing in a solution of our dye(s).

Photographic silver halide emulsions, such as those listed above, containing the sensitizing dyes of our invention can also contain such addenda as chemical sensitizers, e.g. sulfur sensitizers (e.g. allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.g. potassium chloroaurate, auric trichloride, etc.) (see US. Patents 2,540,085; 2,597,856 and 2,597,- 915), various palladium compounds, such as palladium chloride (U.S. 2,540,086), potassium chloropalladate (U.S. 2,598,079), etc., or mixtures of such sensitize-rs; antifoggants, such as ammonium chloroplatinate (U.S. 2,556,245), ammonium chloroplantinite (U.S. 2,566,263), benzotriazole, nitrobenzimidazole, 5-nitroindazole, benzidine, mercaptans, etc. (see Mees, The Theory of the Photographic Process, Macmillan pub., page 460), or mixtures thereof; hardeners, such as formaldehyde (U.S. 1,763,533), chrome alum (U.S. 1,763,533), glyoxal (U.S. 1,870,354, dibromacrolein (Br. 406,750), etc.; color couplers, such as those described in US. Patent 2,423,730, Spence and Carroll US. application 771,380, filed Aug. 29, 1947 (now US. Patent 2,640,776), etc.; or mixtures of such addenda. Dispersing agents for color couplers, such as those set forth .in U.S. Patents 2,322,027 and 2,304,940, can also be employed in the above-described emulsions.

Our emulsions are coated to advantage on any of the materials used for photographic elements including, for example, paper, glass, cellulose acetate, cellulose nitrate, synthetic film forming resins, e.g., the polyesters, the polyamides, polystyrenes, etc.

The following examples will serve to further illustrate our invention by showing the sensitizing effects of representative dyes of our invention on silver halide emulsions.

EXAMPLE 1 Portions of a gelatino silver bromoiodide emulsion containing 0.77 mole percent iodide of the type described by Trivelli and Smith, Phot. Journal, 79, 330 (1939) were sensitized by adding a solution of the indicated dye in a suitable solvent. The sensitized emulsions were coated at a coverage of 432 mg. of silver per square foot on a cellulose acetate film support. A sample of each coating was exposed on an Eastman 1B Sensitometer (an intensity scale Sensitometer), and on a wedge spectrograph, processed for three minutes in Kodak Developer D19, fixed in a conventional sodium thiosulfate fix, washed and dried. Table 1 summarizes the spectral sensitization data obtained.

TABLE 1 Spectral Sensitization Dye Number Max, 111p Range, m

Similarly, it can be shown that these and other complex cyanine dyes of our invention are used to advantage to sensitize other hydrophilic colloid silver halide emulsions.

EXAMPLE 2 A portion of a silver bromoiodide emulsion as described in Example 1 and a portion of a silver chlorobromide emulsion containing 40 mole percent bromide were sensitized as specified in Table 2.

The dyes were added as solutions in a suitable solvent. The coatings were exposed, processed, and evaluated as in Example 1. The results are summarized in Table 2.

EXAMPLE 3 Example 1 was repeated using dyes 9, 10, 11 and 12 in place of dyes 1, 2, and 3. The results are summarized in Table 3.

TABLE 3 Spectral Sensitization Dye Number Max, 11] Range, my

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can and III

I x I 14 m represents an integer of from 1 to 2; Q represents a group selected from the class consisting of a group, a

wherein R and R each represents an alkyl group; Z and Z each represent the nonmetallic atoms necessary to complete a 5 to 6 member heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a henzothiazole nucleus, a naphthothiazole nucleus, a thianaphtheno- 7, 6', 4, S-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a thiazoline nucleus, a Z-pyridine nucleus, a 4- pyridine nucleus, a 2-quinoline nucleus, a 4-quinoline nucleus, a l-isoquinoline nucleus, a 3-isoquinoline nucleus, a 3,3-dialkylindolenine nucleus, an imidazole nucleus, a benzi-midazole nucleus, and a naphthimidazole nucleus; j represents an integer of from 1 to 2; R represents a member selected from the class consisting of the hydrogen atom, an alkyl group, an an aryl group; n represents an integer of from 1 to 4; Y and Y each represent a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, a

/Ra 2)ugroup; a

CHaCH:

group, and a CHaCHg group, such that at least one of the groups Y and Y contains a group with a tertiary nitrogen atom; q represents an integer of from 2 to 4; R R and R each represents an alkyl group; W and -W each represent a group selected from the class consisting of the oxygen atom, the sulfur atom, the selenium atom and a NR group wherein R represents a group selected from the class consisting of an alkyl group and an aryl group; p represents an integer of from 1 to 2; X represents an acid group; D and D each represent a group selected from the class consisting of the sulfur atom, the selenium atom and the oxygen atom;

group, a

group, a

. N -C 4:, ll

group and a -C-N-C- ll l. ll,

group; and R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, an amino group, a carbonamido group, a sulfonamido group, a sulfamly group, and a carbamyl group.

2. A light-sensitive photographic element of claim 1 in which the said dye is contiguous with the said silver halide grains.

3. A light-sensitive photographic element of claim 1 in which the dye is selected from those having Formula I.

4. A light-sensitive photographic elementof claim 1 in which the dye is selected from those having Formula II.

5. A light-sensitive photographic element of claim 1 in which the dye is selected from those having Formula HI.

6. A light-sensitive photographic element having at least one hydrophilic colloid silver halide emulsion layer containing 2-[(2-benzothiazolylethoperchlorate) methylene]- 3-(3-dimethylaminopropyl) 5 l-methylnaphtho[l,2- d] -thiazolin 2 ylidene)-l-phenylethylidene]-4-thiazolidinone.

7. A light-sensitive photographic element having at least one hydrophilic colloid silver halide emulsion layer containing 2 [(5 chloro-2-benzothiazolylethoperchlorate)- methylene]-(3-dimethylaminopropyl) 5 [(1 methylnaphtho(l,2 d] thiazolin-Z-ylidene)-1-phenylethylidene]- 4-thiazolidinone.

8. A light-sensitive photographic element having at least one hydrophilic colloid silver halide emulsion layer containing l-(2-diethylaminoethyl) 5- [(1 ethylnapht-ho [1,2-d]thiazolin 2 ylidene)-(1methylnaphthol[1,2-d]- thiazolin-Z-ylidene)isopropylidene] 3 phenylbarbituric acid.

9. A light-sensitive photographic element having at least one hydrophilic colloid silver halide emulsion layer con- References Cited Mining 1 (2 diethylaminoethyl)-5-[di(l-ethylnaphtho- [1,2 d] thiazolin 2 ylidene)isopr0pylidene-3-pheny1- UNITED STTATES PATENTS barbitulric acid 1 2,304,981 12/1942 W11manns 96106 10. A light-sensitive photographic element having at 5 2,870,014 1/1959. at 96 '1O6 least one hydrophilic colloid silver halide emulsion layer 2,895,955 7/1959 Haseltma et containing 5 [(1 ethylnaphth0l[l,2 d]thiaz0lin 2- 2,984,664 5/1961 Fry et IMG 2405 ylidene) 1 phenylethylene]-3-(2-morpholinoethyl)-2- [3 (2 morpholinoethyl) 4 oX0-2-thioxo-5-thiazoli- NORMAN TORCHIN P'lmary Examiner dinylidene]-4-thiazolidinone. 10 J. T. BROWN, Assistant Examiner.

P0-1050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. s 335 1 Dated 8 August 1967 Inventor) Robert C. Taber and Leslie G. S Brooker It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 70, the word "strain" should read stain Column P, line 17, after "propylsulfamoy, insert phenylsulfamoyl Column line +0, insert formula:

Column 1-, line &4, cancel "formula:".

Column l, lines 71-75 0 0 J! a =c \N-Y of formula VI: should be c n-a Column 5, line 12, insert the word the at the beginning of the line.

Column 6, line 49, "odod" should read odor Column 9, line il, "obtained 21%" should read obtained (21% Column 9, line 54, "2. 8 g. should read l2. 8 g.

P0-105O UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. ,335, Dated 8 August 1-967 Inventor) Robert C. Taber and Leslie G.S. Brooker It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 13, line 6, the word "containng" should read containing should read Column 13, line 7, the word "coloid" should read colloid Column 1 line 67, place a I in front of (l,2- d 7.

Signed and sealed this 11th day of May 1971.

USEAL) Attest:

EDWARD M.FLETCHER,J'R. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

1. A LIGHT-SENSITIVE PHOTOGRAPHIC ELEMENT HAVING AT LEAST ONE HYDROPHILIC COLLOID LAYER CONTAINING SILVER HALIDE GRAINS AND AT LEAST ONE HYDROPHILIC COLOID LAYER CONTAINING A DYE SELECTED FROM THOSE HAVING THE FORMULAS: 